Polyether polyamine agents and mixtures thereof

ABSTRACT

Provided herein are polyamine precursors useful in the manufacture of epoxy resins. Use of a polyamine precursor according to the invention provides an epoxy resin formulation having an increased working time over prior art amines used for curing epoxies. Increased working times translate to the ability to manufacture composites which could not be made using conventional epoxy curing agents, such as composite blades for wind-driven turbines. Such polyamines are also useful in polyurea formulations for lengthening reaction time, thus allowing more flow of applied polyurea coatings prior to gellation.

CROSS-REFERENCES TO RELATED APPLICATIONS

This application is a divisional application of then U.S. applicationSer. No. 10/524,247, which was filed Feb. 10, 2005 and has now issued asU.S. Pat. No. 7,550,550, which was the National Phase of InternationalApplication PCT/US03/27082, filed Aug. 29, 2003, which designated theU.S. and was published in English and which claims priority toProvisional Application No. 60/407,112 filed Aug. 30, 2002, and U.S.Provisional Application No. 60/409,492 filed Sep. 10, 2002. The notedapplications are herein incorporated by reference.

FIELD OF THE INVENTION

The present invention relates to epoxy resins. More particularly itrelates to amine curing agents useful in curing epoxy resins. Moreparticularly still, the invention relates to amine curing agents whichdisplay reduced reactivity as a curing agent, which translates to anincreased “working time” associated with the manufacture of articlesfrom epoxy resins.

BACKGROUND INFORMATION

Manufacturing processes commonly used in conjunction with the productionof epoxies include filament winding, pultrusion, infusion molding, resintransfer molding (RTM), vacuum assisted RTM (VARTM), and wet lay-up orvacuum bag techniques. Polyoxyalkylene amines, or “polyetheramines” asthey are sometimes called, are useful as curing agents in epoxy systemsto improve flexibility, and to lengthen working time in the manufactureof fiber-reinforced composites. The “working time” is defined as thetime period between when the reactive components of the epoxy resin arefirst mixed with one another and when the mixture is no longer suitablefor processing. During the working time, the resin or article containingthe resin remains in a pourable, flexible, pliable or otherwisemouldable form.

The use of epoxy binders is preferred by many manufacturers offiber-reinforced composite wind turbine generator (“WTG”) propellers,which propellers each typically comprise three individualepoxy-composite blades having lengths from 20-40 meters each.Unfortunately, the working times provided for by currently-availableamine curing agents are insufficient for the preparation of bladeshaving optimal properties. In addition to a longer working time, thematerials from which a WTG blade material is made must also maintaingood heat resistance when cured.

Many WTG blade manufacturers today use the VARTM process when workingwith liquid epoxy systems or epoxy polyester systems. These resinsystems must cure slowly in a controlled fashion and allow sufficientworking time to wet-out the fiberglass, aramid fiber, carbon fiber, orother fibers that are used as reinforcing materials in the wind turbineblades. In some cases, prepreg epoxy systems may be used. In theseinstances, fibers pre-impregnated with a reasonably latent epoxy resinsystem may be used to form the turbine blade. The use of polyetheraminesas epoxy curing agents is not common in the prepreg materials, but iscommon practice by some using VARTM and other liquid molding processes,where JEFFAMINE® D-230 amine (Huntsman Corporation, Houston, Tex.) isused in large quantities. However, manufacturers understand that theworking time for using such materials is too short for optimumproduction, mainly when manufacturing individual blades of greater than30 meters in length. Since the tendency in the WTG industry is to go tolonger blade length to increase the ability of each WTG to produce morepower/unit, a need has arisen in the art for curing agents which canmake the manufacture of such blades commercially viable.

SUMMARY OF THE INVENTION

The present invention provides polyamines useful as a curing agent inepoxy resins having the structure:

wherein L is an oxyalkoxo group having the structure:

in which R₁ is any group selected from the group consisting of: C₁ to C₅alkylene; 2-methyl propylene; 2,2-dimethyl propylene; —CH₂CH₂—O—CH₂CH₂—;—CH₂CH₂CH₂—O—CH₂CH₂CH₂—; the group

The invention also includes a process for preparing a cured epoxy resincomprising the steps of: a) providing a polyamine per the above, ormixtures thereof with each other or with one or more materials selectedfrom the group consisting of: N-aminoethylpiperazine;diethylenetriamine; triethylenetetramine; tetraethylenepentamine;2-methylpentamethylene; 1,3-pentanediamine trimethylhexamethylenediamine; a polyamide; a polyamidoamine; a Mannich-base type hardener;bis(aminomethyl)cyclohexylamine; isophorone diamine; menthane diamine;bis(p-aminocyclohexyl)methane; 2,2′-dimethylbis(p-aminocyclohexyl)methane; dimethyldicyclohexylmethane);1,2-diaminocyclohexane; 1,4-diaminocyclohexane; meta-xylene diamine;norbornanediamine; meta-phenylene diamine; diaminodiphenylsulfone;methylene dianiline; JEFFAMINE® D-230; JEFFAMINE® D-400; JEFFAMINE®T-403; and diethyltoluenediamine;

-   b) providing an epoxy precursor comprising a material having at    least two epoxy end groups; and-   c) contacting said epoxy precursor and said polyamine with one    another.

Suitable polyfunctional epoxy precursors are those which have at leasttwo epoxy end groups and include the following:

in which n may be any integer between 0 and about 4; DGEBF(diglycidylether of bisphenol F) having the following structure:

such as D.E.R.(R) 354 epoxy resin from The Dow Chemical Company; andtri-functional epoxy resins such as TACTIX(R) 742 epoxy from HuntsmanApplied Materials:

Higher functional epoxy resins such as epoxy novolacs (D.E.N.® 438 epoxyresin, ARALDITE® EPN 1180 epoxy NOVOLAC D.E.N.® 431 epoxy resin are alsosuitable for use in a process according to the present invention. Allmaterials which contain at least two epoxy groups in their molecularstructure are suitable for use in this invention, including withoutlimitation those described above, and such materials are convenientlyreferred to as “polyfunctional epoxy precursor” in the claims appendedhereto.

DETAILED DESCRIPTION OF THE INVENTION

This invention involves the preparation of hindered polyetheramines. Italso relates to the use of hindered polyetheramines for curing standardepoxy resins. An epoxy resin cured using a polyetheramine according tothe invention has a longer working time those made using prior art aminecuring agents.

The present invention provides primary polyetherdiamines andpolyethertriamines which are preferably prepared by reductive aminationof alcohols such as those in formulae (III)-(XI) below:

According to one preferred form of the invention, a polyol according tothose specified in formulae (III)-(XI) is first prepared viaalkoxylation of a suitable initiator. The reaction may be carried out byheating the initiator and the corresponding higher alkyl-substitutedoxirane in a closed reaction vessel at relatively low pressures.Reaction temperatures of 100-110° C. are used in the presence of a basecatalyst, such as a tertiary amine or alkali metal hydroxide for severalhours. Then the mixture is vacuum stripped of any excess unreactedoxirane and the catalyst to leave the resulting polyol mixture. It ispreferred that polyols of the invention be prepared wholly or partiallyfrom oxiranes, having alkyl groups with carbon numbers of C₂ to C₁₀. Thealkyl group may be branched or linear in structure. One preferred andmore readily available oxirane in this class is 1,2-butylene oxide,which may be self-polymerized with base catalysts, using water as aninitiator, to produce low-molecular weight polyoxybutylene diols orglycerin as an initiator to produce similar triols of 200-400 MW.Polyols with larger pendant alkyl groups would have more steric crowdingabout the mainly secondary hydroxyl groups at the end of the polyolchains. A mixture of oxiranes may also be used in the process of polyolpreparation, but the oxirane of higher alkyl substitution should beadded on to the end of each polyol chain prior to the neutralization andreductive amination steps. Examples of other oxiranes to be used in theinternal polyol backbone are ethylene oxide and propylene oxide. Thus,the starting materials for the polyol precursors of the polyamines ofthe invention may consist of 1,2-glycols, such as ethylene glycol andpropylene glycol, or higher diols, such as diethylene glycol ordipropylene glycol. In addition, longer carbon chain diols, such as1,3-propanediol, 1,4-butanediol or 1,6-hexanediol may be used asstarting material for the addition of the higher oxirane to prepare thehindered polyols for reductive amination to the hinderedpolyetheramines. Multifunctional initiators, such as glycerin,trimethylol-propane (TMP), pentaerythritol, and alpha methyl glucoside(AMG), may also be alkoxylated with the higher oxiranes to preparepolyols for reductive amination. After neutralization, the polyols maybe purified by distillation, and subsequently aminated reductively inthe presence of hydrogen and excess ammonia at pressures up to 2000 psiand temperatures about or in excess of 200° C. using a suitable metalcatalyst as described by Yeakey et al. 1). Examples of the preferredpreparatory methods for these polyols are now set forth.

Polyol (Formula III)-Ethylene Glycol+Butyleneoxide

To a dry, nitrogen purged reactor were added 2500 grams of ethyleneglycol and 12.5 grams of 1,1,3,3,-tetramethylguanidine (TMG). 5809 gramsbutyleneoxide were then added while agitating. The kettle was thenheated to 80° C. and temperature control was initiated. The kettle wasthen held at 80° C. for 10 hours, followed by an additional 10 hours at100° C. The product was then stripped for one hour at 100° C. usingnitrogen and the product was then collected. The reaction was followedby gas chromatography during the process.

Polyol (Formula IV)-Propanediol+Butyleneoxide

To a dry, nitrogen purged reactor were added 2500 grams of propanedioland 12.5 grams of 1,1,3,3,-tetramethylguanidine (TMG). 4270 gramsbutyleneoxide were then added while agitating. The kettle was thenheated to 80° C. and temperature control was initiated. The kettle wasthen held at 80° C. for 10 hours, followed by an additional 10 hours at100° C. The product was then stripped for one hour at 100° C. usingnitrogen and the product was then collected. The reaction was followedby gas chromatography during the process.

Polyol (Formula V)-2-Methyl-1,3-Propanediol+Butyleneoxide

To a dry, nitrogen purged reactor were added 2000 grams of2-methyl-1,3-propanediol and 10.0 grams of 1,1,3,3,-tetramethylguanidine(TMG). 3361 grams butyleneoxide were then added while agitating. Thekettle was then heated to 80° C. and temperature control was initiated.The kettle was then held at 80° C. for 10 hours, followed by anadditional 10 hours at 100° C. The product was then stripped for onehour at 100° C. using nitrogen and the product was then collected. Thereaction was followed by gas chromatography during the process.

Polyol (Formula VI)-1,4-Butanediol+Butyleneoxide

To a dry, nitrogen purged reactor were added 3000 grams of1,4-butanediol and 30.0 grams of potassium hydroxide as catalyst. 4321grams butyleneoxide were then added while agitating. The kettle was thenheated to 80° C. and temperature control was initiated. The kettle wasthen held at 80° C. for 10 hours, followed by an additional 10 hours at100° C. The product was then stripped for one hour at 100° C. usingnitrogen and the product was then collected. The reaction was followedby gas chromatography during the process.

Polyol (Formula VII)-Diethylene Glycol+Butyleneoxide

To a dry, nitrogen purged reactor were added 2500 grams of diethyleneglycol and 12.5 grams of 1,1,3,3,-tetramethylguanidine (TMG). 2973 gramsbutyleneoxide were then added while agitating. The kettle was thenheated to 80° C. and temperature control was initiated. The kettle wasthen held at 80° C. for 10 hours, followed by an additional 10 hours at100° C. The product was then stripped for one hour at 100° C. usingnitrogen and the product was then collected. The reaction was followedby gas chromatography during the process.

Polyol (Formula VIII)-Trimethylolpropane+Butyleneoxide

To a dry, nitrogen purged reactor were added 2268 grams of1,1,1-trimethylolpropane and 11.34 grams of1,1,3,3,-tetramethylguanidine (TMG) as catalyst. 4266 gramsbutyleneoxide were then added while agitating. The kettle was thenheated to 80° C. and temperature control was initiated. The kettle wasthen held at 80° C. for 10 hours, followed by an additional 10 hours at100° C. The product was then stripped for one hour at 100° C. usingnitrogen and the product was then collected. The reaction was followedby gas chromatography during the process.

Polyol (Formula X)-Tris(hydroxymethyl)ethane+Butyleneoxide

To a dry, nitrogen purged reactor were added 2500 grams oftris(hydroxymethyl)ethane and 12.5 grams of1,1,3,3,-tetramethylguanidine (TMG). 6002 grams butyleneoxide were thenadded while agitating. The kettle was then heated to 80° C. andtemperature control was initiated. The kettle was then held at 80° C.for 10 hours, followed by an additional 10 hours at 100° C. The productwas then stripped for one hour at 100° C. using nitrogen and the productwas then collected. The reaction was followed by gas chromatographyduring the process.

Conversion of Butoxylates to Amines

The polyols in formulas (III)-(XI) above were reductively aminated usingammonia to the corresponding amines in a 100 cc continuous unit using acatalyst as described in U.S. Pat. Nos. 3,151,112 and 3,654,370. Thecatalyst, in the form of ⅛×⅛ inch tablets, was charged to the 100 cctubular reactor. The polyol and ammonia were pumped separately and mixedin-line with hydrogen and fed through the catalyst bed. The polyol andammonia were kept in an approximate 1:1 wt feed ratio, while the ammoniato hydrogen mole ratio was kept at about 20:1. The reactor pressure washeld at about 2000 psig and the temperature was maintained at about 220°C. The polyol and ammonia feed rates used in each run varied betweenabout 65 g/hr to 100 g/hr. The products were collected over 2-3 days andstripped of excess ammonia, water and light amines. In some of theamination runs, the material was passed through the reactor a secondtime to bring up the amine level in the product. Reductive amination ofthese polyols yields the polyamines having predominantly the structuresshown below in formulae (XII)-(XX) below:

Thus, the polyamine of formula XII is represented by formulas (I) and(II) wherein R₁ is an ethylene group. The polyamine of formula XIII isrepresented by formulas (I) and (II) wherein R₁ is a propylene group.The polyamine of formula XIV is represented by formulas (I) and (II)wherein R₁ is a 2-methyl propylene group. The polyamine of formula XV isrepresented by formulas (I) and (II) wherein R₁ is a butylene group. Thepolyamine of formula XVI is represented by formulas (I) and (II) whereinR₁

is a —CH2CH2—O—CH2CH2— group. The polyamine of formula XVII isrepresented by formulas (I) and (II) wherein R₁ is a group.

The polyamine of formula XVIII is represented by formulas (I) and (II)wherein R₁ is a

group. The polyamine of formula XIX is represented by formulas (I) and(II) wherein R₁ is a

group. The polyamine of formula XX is represented by formulas (I) and(II) wherein R₁ is a 2,2-dimethyl propylene group.

The gel times of an epoxy blend are longer for amines having ethylgroups on the carbon atom alpha to the amine vs. those having methylgroups on the carbon atom alpha to the amine. The polyetheramines of theinvention offer more than 50% longer working time, when used to curestandard epoxy resins than is afforded using amine curing agents of theprior art. We were surprised to find that some of the polyetheraminestook almost twice as long to cure epoxy resins as the standard productsnow used in the current wind blade manufacture, specifically, the amineof formula XIV.

Conditions useful for preparing a composition relating to the presentinvention include: A temperature range of 50-120° C. for the polyolpreparations; and 180-220° C. for the reductive amination of polyols.The useful pressures are: 40-100 psi for the polyol preparations, and1500-2500 psi for the reductive aminations.

A polyamine according to the formulas (XII) through (XX) can be reactedwith an organic di-isocyanate to form a polyurea. These di-isocyanatesinclude standard isocyanate compositions known to those skilled in theart. Preferred examples of di-isocyanates include MDI-based quasiprepolymers such as those available commercially as RUBINATE® 9480,RUBINATE® 9484, and RUBINATE® 9495 from Huntsman International, LLC.Liquified MDI such as MONDUR® ML may be used as all or part of theisocyanate. The isocyanates employed in component (A) are generallyknown to one skilled in the art. Thus, for instance, they can includealiphatic isocyanates of the type described in U.S. Pat. No. 4,748,192.Accordingly, they are typically aliphatic diisocyanates and, moreparticularly, are the trimerized or the biuretic form of an aliphaticdiisocyanate, such as hexamethylene diisocyanate, or the bifunctionalmonomer of the tetraalkyl xylene diisocyanate, such as the tetramethylxylene diisocyanate. Cyclohexane diisocyanate is also to be considered apreferred aliphatic isocyanate. Other useful aliphatic polyisocyanatesare described in U.S. Pat. No. 4,705,814 which is fully incorporatedherein by reference thereto. They include aliphatic diisocyanates, forexample, alkylene diisocyanates with 4 to 12 carbon atoms in thealkylene radical, such as 1,12-dodecane diisocyanate and1,4-tetramethylene diisocyanate. Also described are cycloaliphaticdiisocyanates, such as 1,3 and 1,4-cyclohexane diisocyanate as well asany desired mixture of these isomers,1-isocyanato-3,3,5-trimethyl-5-isocyanato methylcyclohexane (isophoronediisocyanate); 4,4′-,2,2′- and 2,4′-dicyclohexylmethane diisocyanate aswell as the corresponding isomer mixtures, and the like. Further, a widevariety of aromatic polyisocyanates may be used to form the foamedpolyurea elastomer of the present invention. Typical aromaticpolyisocyanates include p-phenylene diisocyanate, polymethylenepolyphenylisocyanate, 2,6-toluene diisocyanate, dianisidinediisocyanate, bitolylene diisocyanate, naphthalene-1,4-diisocyanate,bis(4-isocyanatophenyl)methane,bis(3-methyl-3-iso-cyanatophenyl)methane,bis(3-methyl-4-isocyanatophenyl)methane, and 4,4′-diphenylpropanediisocyanate. Other aromatic polyisocyanates used in the practice of theinvention are methylene-bridged polyphenyl polyisocyanate mixtures whichhave a functionality of from about 2 to about 4. These latter isocyanatecompounds are generally produced by the phosgenation of correspondingmethylene bridged polyphenyl polyamines, which are conventionallyproduced by the reaction of formaldehyde and primary aromatic amines,such as aniline, in the presence of hydrochloric acid and/or otheracidic catalysts. Known processes for preparing polyamines andcorresponding methylene-bridged polyphenyl polyisocyanates therefrom aredescribed in the literature and in many patents, for example, U.S. Pat.Nos. 2,683,730; 2,950,263; 3,012,008; 3,344,162 and 3,362,979, all ofwhich are fully incorporated herein by reference thereto. Usually,methylene-bridged polyphenyl polyisocyanate mixtures contain about 20 toabout 100 weight percent methylene diphenyldiisocyanate isomers, withthe remainder being polymethylene polyphenyl diisocyanates having higherfunctionalities and higher molecular weights. Typical of these arepolyphenyl polyisocyanate mixtures containing about 20 to about 100weight percent diphenyldiisocyanate isomers, of which about 20 to about95 weight percent thereof is the 4,4′-isomer with the remainder beingpolymethylene polyphenyl polyisocyanates of higher molecular weight andfunctionality that have an average functionality of from about 2.1 toabout 3.5. These isocyanate mixtures are known, commercially availablematerials and can be prepared by the process described in U.S. Pat. No.3,362,979. A preferred aromatic polyisocyanate is methylenebis(4-phenylisocyanate) or “MDI”. Pure MDI, quasi-prepolymers of MDI,modified pure MDI, etc. are useful to prepare a polyurea according tothe invention. Since pure MDI is a solid and, thus, often inconvenientto use, liquid products based on MDI or methylenebis(4-phenylisocyanate) are used herein. U.S. Pat. No. 3,394,164,incorporated herein by reference thereto, describes a liquid MDIproduct. More generally, uretonimine modified pure MDI is included also.This product is made by heating pure distilled MDI in the presence of acatalyst. The liquid product is a mixture of pure MDI and modified MDI.The term isocyanate also includes quasi-prepolymers of isocyanates orpolyisocyanates with active hydrogen containing materials. “Organicdi-isocyanate” as used herein includes all of the foregoing isocyanates.

In addition to the use of the pure polyamines shown above in formulae(XII)-(XX), the present invention contemplates the use of these aminesin each combinations with one another, and with amines of the prior art.Amines of the prior art useful in combination with those of formulae(XII)-(XX) include, without limitation: N-aminoethylpiperazine (“AEP”);diethylenetriamine (“DETA”); triethylenetetramine (“TETA”);tetraethylenepentamine (“TEPA”); 2-methylpentamethylene diamine (Dytek®A-DuPont); 1,3-pentanediamine (Dytek®EP-DuPont); trimethylhexamethylenediamine (1:1 mix of 2,2,4-, and 2,4,4-isomers is called Vestamin®TMD-Creanova); polyamide hardeners; polyamidoamine hardeners;Mannich-base type hardeners; bis(aminomethyl)cyclohexylamine(“1,3-BAC”); isophorone diamine (“IPDA”); menthane diamine;bis(p-aminocyclohexyl)methane (“PACM”); 2,2′-dimethylbis(p-aminocyclohexyl)methane (“DMDC”); dimethyldicyclohexylmethane);1,2-diaminocyclohexane (“DACH”); 1,4-diaminocyclohexane (“DACH”);meta-xylene diamine (“m-XDA”); norbornanediamine (“NBDA”);meta-phenylene diamine (“m-PDA”); diaminodiphenylsulfone (“DDS” or“DADS”); methylene dianiline (“MDA”); JEFFAMINE® D-230 (Huntsman);JEFFAMINE® D-400 (Huntsman); JEFFAMINE® T-403 (Huntsman); anddiethyltoluenediamine (“DETDA”).

The amines, combinations, and processes provided herein are particularlybeneficial in providing epoxy systems having an increased cure time overcompositions and processes of the prior art. During the manufacture ofparticular composite articles, such as wind turbine blades, a longcuring time is desirable in order to enable the actively curing resin topenetrate the interstices of the fibers which are part of the composite,while also permitting enough time for molding to place all the materialin its desired location. It is often desirable for the resin/catalystmixture to remain at a viscosity of less than 1000 centipoise at 25degrees C. for 8 hours.

Consideration must be given to the fact that although this invention hasbeen described and disclosed in relation to certain preferredembodiments, obvious equivalent modifications and alterations thereofwill become apparent to one of ordinary skill in this art upon readingand understanding this specification and the claims appended hereto.Accordingly, the presently disclosed invention is intended to cover allsuch modifications and alterations, and is limited only by the scope ofthe claims which follow.

1. A polyamine composition having the structure:

wherein L is an oxyalkoxo group having the structure:—O—R₁—O— in which R₁ comprises at least one of 2-methyl propylene;2,2-dimethyl propylene; and mixtures thereof; and wherein R₁ may furthercomprise a group selected from the group consisting of: C₁ to C₅alkylene; —CH₂CH₂—O—CH₂CH₂—; —CH₂CH₂CH₂—O—CH₂CH₂CH₂—;

including mixtures of two or more of the foregoing polyamines.
 2. Aprocess for preparing a cured epoxy (poly-(etheralkanolamine)) resincomprising the steps of: a) providing a polyamine composition accordingto claim 1; b) providing a polyfunctional epoxy precursor; and c)contacting said polyfunctional epoxy precursor and said polyamine withone another.
 3. A process for preparing a polyurea comprising the stepsof: a) providing an organic di-isocyanate; b) providing at least onepolyamine composition according to claim 1; and c) contacting saidorganic di-isocyanate and said polyamine with one another.
 4. A processfor preparing a cured epoxy (poly-(etheralkanolamine)) resin comprisingthe steps of: a) providing an amine mixture comprising a polyaminecomposition according to claim 1, and one or more materials selectedfrom the group consisting of: N-amino ethylpiperazine;diethylenetriamine; triethylenetetramine; tetraethylenepentamine;2-methylpentamethylene;1,3-pentanediamine ; trimethylhexamethylenediamine; a polyamide hardener; a polyamidoamine hardener; a Mannich-basehardener; bis(aminomethyl)cyclohexylamine; isophorone diamine; menthanediamine; bis(p-aminocyclohexyl)methane; 2,2′-dimethylbis(p-aminocyclohexyl) methane; dimethyldicyclohexylmethane;1,2-diaminocyclohexane; 1,4-diaminocyclohexane; meta-xylene diamine;norbornanediamine; meta-phenylene diamine; diaminodiphenylsulfone;methylene dianiline; JEFFAMINE® D-230 amine; JEFFAMINE® D-400 amine;JEFFAMINE® T-403 amine; and diethyltoluenediamine; b) providing anpolyfunctional epoxy; and c) contacting said polyfunctional epoxyprecursor and said polyamine with one another.
 5. A process forpreparing a polyurea comprising the steps of: a) providing an organicdi-isocyanate; b) providing a polyamine according to claim 1 inadmixture with at least one material selected from the group consistingof: N-aminoethylpiperazine; diethylenetriamine; triethylenetetramine;tetraethylenepentamine; 2-methylpentamethylenediamine;1,3-pentanediamine; trimethylhexamethylene diamine; polyamidehardeners; polyamidoamine hardeners; Mannich-base hardeners;bis(aminomethyl) cyclohexylamine; isophorone diamine; menthane diamine;bis(p-aminocyclohexyl) methane (“PACM”); 2,2′-dimethylbis(p-aminocyclohexyl) methane;dimethyldicyclohexylmethane;1,2-diaminocyclohexane; 1,4-diaminocyclohexane; meta-xylene;norbornanediamine; meta-phenylene diamine; diaminodiphenylsulfone;methylene dianiline; JEFFAMINE® D-230 amine; JEFFAMINE® D-400 amine;JEFFAMINE® T-403 amine; and diethyltoluenediamine; and c) contactingsaid organic di-isocyanate and said polyamine with one another.
 6. Thepolyamine composition of claim 1, wherein the R₁ further comprises atleast one of a C₁ to C₅ alkylene and mixtures thereof.
 7. The polyaminecomposition of claim 1, wherein the R₁ further comprises at least one of—CH₂CH₂—O—CH₂CH₂—; —CH₂CH₂CH₂—O—CH₂CH₂CH₂—; and mixtures thereof.
 8. Thepolyamine composition of claim 1, wherein the R₁ further comprises atleast one of the following:

including mixtures of two or more of the foregoing polyamines.